Method of dyeing cellulosic fibers



Patented Apr. 29, 1952 UNITED STATE srATENT OFF assesos ICE METHOD OFDYEING CELLULOS IC FIBERS WITH DIFFICULTLY WATER- SOLUBLE COPPERCOMPOUNDS OF DYESTUFFS USING A COPPER-FREE DYESTUFF, AN ALIPHATIC AMINE,AND A COMPLEX COP- PER COMPOUND OF AN ALIPHATIC HY DROXYCARBOXYLIC ACIDHenri Riat, Walter Anderau, Jacques Wegniann,

Hans Mayer, and Karl Menzi, Basel, Switzerland, assignors to CibaLimited, Basel, Switzerland, a Swiss firm No Drawing. ApplicationSeptember 29, 1949, Se-

rial No. 118,714. In Switzerland October 8,

of value which in the copper-free condition are soluble in water and aresuitable for the dyeing of cellulosic materials, but which with coppersalts in the absence of organic bases give difficultly soluble complexcopper compounds which, on account of this property, are not well suitedto dyeing purposes, at all events when the intention is to avoid dyeing"from a suspension, which method as a rule leads to unsatisfactoryresults.

Those dyestuffs are of advantage for dyeing Z twice and in symmetricalform, as for example those having the atom grouping X I I N=NO wherein Xindicates'a carboxyl or hydroxyl group and Y a bridge member, as forexample 0 N=N, N-/\\N- NH-COI-IN- or advantageously a direct bondbetween the two benzene nuclei.

Valuable results are also obtained according to the present process withdyestuffs which contain the atom grouping OH OH I twherein Y indicates anitrogen-containing bridge member; and further also with dyestuffs whichaccording to the present process which contain exhibit the atom groupingin the molecule at least two azo groups and at least once the atomgrouping wherein X indicates a carboxyl group or a hydroxyl group, andwherein A represents an aromatic radical and B a cyclic, for example, an

HOaS

HO N:

aromatic or heterocyclic radical, of which radicals the carbon atomsshown form part of the ring structure. Among dyestuffs of thisconstitution those are of special value, for example. which contain thejust mentioned atom grouping SOsH (wherein Z stands for N=N-or OH H H?RH H? Hols For preparation of the dyebaths according to the presentprocess ammonia or water-soluble organic bases are employed. For thispurpose such water-soluble bases are primarily suitable as cannot beremoved with steam, such as aliphatic amines containing hydroxyl groups.As examples of bases there may be mentioned: methylamine, ethylamine,n-propylamine, n-butylamine, n-amylamine, cyclohexylamine,ethylene-diamine, a-amino-,B-diethylamino-ethane, diethylamine,mono-ethanolamine, diethanolamine, triethanolamine, propanolamines,butanolamines, n-butyl-ethanolamine, morpholine and oxyethylmorpholine.Also two or more different bases may be employed at the same time.

As agents yielding copper which are employed according to the presentprocess for the production of dyebaths, there come into considerationfor example copper salts. When simply constituted copper salts areemployed, as for example the sulfate, nitrate or acetate, it is ingeneral of advantage to add to the dyebath, as well as the copper salts,further suitable additions which during the dyeing have the capacity fordispersing any copper hydroxide produced. An example of such an additionis the sodium salt of N-methyl- -heptadecyl-benzimidazole sulfonic acid.

With advantage such copper compounds are employed for the preparation ofthe dyebaths, as contain the copper combined in a complex form in theanion. The complex formers, which produce such complex copper compounds,possess in general the property which is advantageous in the presentprocess that they do not withdraw the copper from complex coppercompounds of dyestuffs. As examples of such complex formers there may bementioned: aliphatic amino-carboxylic acids such as glycocoll oralanine, aliphatic hydroxy-carboxylic acids such as glycollic acid,lactic acid, fi-hydroxy-propionic acid, [3- hydroxy-butyric acid,tartaric acid, citric acid.

Instead of adding to the dyebaths the specified copper compounds whichcontain the copper in complex combination in the anion, in the alreadyformed condition, these compounds can also be produced in the dyebathitself by adding to the latter, for example, on the one hand a coppersalt such as copper chloride, sulfate, nitrate, formate or acetate andon the other hand a complex former which is capable of binding thismetal in the anion in a complex manner, for example an alkali salt of analiphatic amino-carboxylic acid or hydroxy-carboxylic acid.

In the preparation of the dyebaths it is suitable to proceed in such amanner that the compound containing copper is added after, or at theearliest at the same time as, the addition is made of the ammonia or theorganic base to the dyebath containing the copper-free dyestuff.Accordingly, for example, the following methods of operation aresuitable: The copper-free dyestuff is first dissolved either in thedyebath itself or in a little water, the concentrated solution beingadded to the dyebath, thereupon ammonia or an organic base is added andfinally the copper compound (for example sodium-copper-tartrate)containing the copper combined in the anion in complex form; oralternatively there is added to the dyebath which contains thecopper-free dyestuff dissolved therein, an aqueous solution consistingof ammonia or the organic base, a copper salt (for example coppersulfate) and a complex former which is capable of binding this metal inthe anion in complex form (for example sodium citrate); or alternativelythere is added to the dyebath which contains the copper-free dyestuffdissolved therein, a solution of ammonia or the organic base and acompound containing the copper combined in the anion in complex form(for example sodium-copper-tartrate) The solutions to be employedaccording to both of the latter methods of operation can be produced asstock solutions ready for use, if desired for storage. In 7 this formthey constitute valuable preparations suitable for the production ofdyebaths.

The quantity of the dyestuif to be employed in the present process canbe varied within wide limits and can be adapted to the desired strengthof the dyeing. The quantity of the ammonia or the organic base issuitably such that at least as much of the base is present, or bettersomewhat more, than is necessary for the formation of the amine complexof the copper. Of the compound which contains the copper there is addedwith advantage an excess over that quantity which is necessary for theformation of the dyestuiicopper complex, which contains per metallisablegroup one atom of copper in complex combination. When for thepreparation of the dyebaths copper salts and complex formers, which arecapable of binding the copper in the anion in complex form, areemployed, it is to be recommended likewise to employ an excess of suchcomplex formers over the quantity necessary for the formation of thecomplex containing the copper in the anion.

In the present process such materials for dyeing are primarily concernedas do not require an acid dyebath but can be dyed from a neutral oradvantageously from an alkaline medium, that is to say cellulosicmaterials such as linen, cotton and artificial silk or staple fiber fromregenerated cellulose. In this case the dyeing can be carried outaccording to the customary known methods for direct-dyeing cellulosedyestuffs, for example with the addition of sodium carbonate and/orsodium sulfate. The bath ratio, i. e. the ratio of the quantity ofmaterial to be dyed to the quantity of dye liquor, is in this processcapable of variation within wide limits-and can to a far reaching extentbe adapted to the requirements of practice. This single-bath andone-stage process gives in the case of the dyestuffs to be employedaccording to the present invention, very uniform and powerful dyeings,which as regards fastness properties at least equal those dyeings whichare obtained with the corresponding metalfree dyestuffs with theapplication of the known after-coppering processes.

Compared with these known processes, as for example the two-bathafter-coppering process with copper sulfate or the one-bathafter-coppering process described in U. S. Patent No. 2,148,659, thepresent process exhibits the advantage that the duration of the dyeingprocess is considerably shortened and that it provides the dyer with amuch better control of the dyeing operation and facilitates dyeing to aparticular shade.

In U. S. Patent No. 2,092,429 a process is described in accordance withwhich products, which may perhaps be considered to be complex compoundsof copper-containing dyestulfs and organic bases, are produced and areemployed for dyeing. According to the methods of operation described inthis prior patent the dyestuifs are always present in the dyebath in adispersed form and there are always obtained dyeings which are weakerthan those which are produced according to the present process.

The following examples illustrate the invention, the parts being byweight unless otherwise stated and the relation between parts by weightand parts by volume being the same as that between the kilogram andliter. Where in the preparation of dyebaths and stocks solutions "wateris mentioned this is to be understood as meaning so called condensedwater (distilled water obtained from live steam).

Example 1 1 part of the dyestuff from 1 mol of tetraz' otised 4:4diaminodiphenyl 3:3 dicarboxylic acid and 2 mols of1-(4-sulfo)-phenyl-3- methyl-5-pyrazolone is treated with parts of hotWater and the whole boiled. By dilution of the stock solution thusobtained with 2900 parts of water at about 60 C. there is produced adyebath to which in addition 2 parts of anhydrous sodium carbonate areadded.

60parts by volume are added to the dyebath, of a solution prepared from50 parts of crystalline copper sulfate, 50 parts of sodium citrate and100 parts of monoethanolamine and which has been diluted with water to1000 parts by volume. Then 100 parts of wetted-out cotton are enteredand the bath temperature is raised within hour to 100 C. Boiling iscarried out for ,5 hour during which, after 5 and after 20 minutesboiling, in each case 20 parts of crystalline sodium sulfate are added.After this time the dyebath is efiectively exhausted. The dyeing issubjected to a cold rinse, in which operation it is advantageous to addto the last rinsing bath 1 part of the condensation product which isobtained when dicyandiamidine is heated for about 10 minutes to 100 C.with four times the quantity of 30 per cent. commercial formaldehyde,the dyeing being allowed to remain in this bath for 5 minutes. The dyematerial is then hydro-extracted and dried. An orange dyeing is obtainedof good iastness to light and washing.

If there is employed for the production of the above mentioned solutionfrom copper sulfate and ethanolamine instead of the 50 parts of sodiumcitrate 30 parts of sodium glycocollate or 50 parts of sodium tartrate,similar results are obtained. The dyeings thus obtained are, both fromthe point of view of colour strength and also of fastness properties, atleast as good as a dyeing obtained according to one of the knownafter-coppering processes. If the same dyeing operation is carried outwithout addition of base, a considerably weaker dyeing results, and ifthe addition of sodium citrate, sodium g-lycocollate or sodium tartrateis omitted, the dyeing may easily become spotted.

A valuable green dyeing is obtained when 100 parts of cotton are dyed,in the manner specified, instead of with the above mentioned dyestuffwith 1 part of the dyestufl of the formula (JOOH S OsNa Example 2' 1part of the dyestuii from 1 molof tetrazotised 4:4 diaminodiphenyl 3:3dicarboxylic acid and 2 mols of 1-(6'-sulfo-2"-naphthyl)3-methyl-5-pyrazolone is dissolved in 100 parts ofwater and by dilutiona dyebath of- 3000 parts by volume produced, to which a further additionis made of 2 parts of anhydrous sodium carbonate.

2,594,803 t V. 9 10 60 parts by volume are added to the dyebath, Example4 of a solution which has been prepared from A dyebath is produced from2900 parts of 100 parts of sodium'copper'tartmte' 200 parts water, 2parts of anhydrous sodium carbonate of monoethanolamme and 1800 parts ofwater and a solution of 1 part of the dyestuff obtained and 100 parts ofwetted-out cotton are entered '5 f a mm 1 mol of tetrazotised 3:3d1hydroxy-4:4- 9 g 13 fi g g g 1;? 28 1 2 diaminodiphenyl and 2 mols of1-(6-sulfo-2- mg our y i g a naphthyl)-3-methyl-5-pyrazolone in 100parts fected dunng A m W operation after of water and 60 parts are addedof a solution 5 and am?! 20 m m each case 20 parts I which has beenproduced from 50 parts of soof crystalline sodium sulfate are added.After 1 dium copper tartrate 100 arts of 6th lene this time the bath iseffectively exhausted and p Y d f amine and 900 parts of water. 100parts of fizg gzig g 53 132 35 yemg 0 good fast wetted-out cotton areentered at about 60 C.

- ff and dyeing is carried out at the boil for hour g i igi i ggggggigigf ggfi ggfjfz after the temperature has been raised to 100diaminodiphenyl, 1 mol of r 1 r p C. /2 hour. After 5 and after mmthyl)3 methyl 5 pymzolone and 1 mol of utes boiling, in each case parts ofcrystalphenyl-S-methyl-5-pyrazolone, there is obtained P sodlum sulfaFef A u brownaccording. to the above directions a powerful 15h dyemgobtained of good fbordeaux dyeing of good fastness to light and E 11955to washmg and g The Same result 15 washing, while t 1 t of t dyestuflfrom also obtained when, instead of 100 parts of 1 mol of tetrazotised3:3'-dihydroXy-4:4-diethylene diamine, 100 parts ofmonoethanolaminodiphenyl, 1 mol of 2-amino-5-hydroxyamine are e p ydnaphthalene-Y-sulfonic acid and 1 mol of 1- a (8 1r 2 hth 1) 3 th 1 5Example 5 su- -o-'-nap y pyrazolone, violet shades likewise of goodfast- 1 part 9 F dyestuff f m of tetrazo' ness properties result-h tised3:3 -d1hydroxy-4:4 -d1am1nod1pheny1 and 2 mols of2-amino-5-hydroxynaphthalene-7- Example 3 sulfonic acid is dissolved in100 parts of water. 1 part of the dyestufi of the formula By dilution ofthis solution to a volume of 3000 siozNHz is dissolved in 100 parts ofwater and added parts and addition of 2 par s of a y ous S0- to adyebath from 2900 parts of water and 2 dium carbonate, a dyebath isproduced to which parts of anhydrous sodium carbonate. 60 parts thefurther addition is made of 60 parts of a of the" complex copper saltsolution described solution which has been prepared from parts inExample 2 are added, 100 parts of wettedof crystalline copper sulfate,50 parts of sodium out cotton are entered at C. and dyeing is tartrate,parts of concentrated ammonia carried out as described in Example 2. The(24 per cent.) and 900 parts of water. bath is cfiectively exhausted andthere results 60 100 parts of Wetted-out cotton are entered a purereddish brown dyeing of excellent fastat a bath temperature of about 60C. and heatness to washing and light. ing to boiling carried out withinhour. vWith- If there is employed 1 part of the dyestuff in the boilingperiod of hour there are added. of the'formula after?) and after 20minutes, in each case 20 NE NH :0 0 N\ l NaOaS- NH(|1/ (l3NH- SO:Na N=Noy N=N H H 1+1; H H

there-is: obtained according to the above procparts of crystallinesodium sulfate. The bath ess'a purejruby, likewise of excellent fastnessisnpractically exhausted. The dyeing is subto washing and light. 7jected to a cold rinse in which in the last rinsing bath with advantage1 part is added to the condensation product which is obtained whendicyandiamidine is heated for about minutes to 100 C. with four timesthe quantity of per cent. commercial formaldehyde. The resulting purereddish blue dyeing exhibits good fastness to washing and. light. Ifthere is employed instead of the sodium tartrate for example 3 parts ofthe sodium salt of N-methyl- -heptadecyl-benzimidazole sulfonic: acid(prepared from commercial stearic acid) and the process is otherwiseconducted in the same way, similar results are obtained.

Example 6 1 part of the dyestufi? from 1 mol of tetrazotised 3 :3-dihydroxy-a 4' -diaminodiphenyl and 2 mols of2-p-hydroxyethylamino-5-hydroxynaphthalene-7-sulfonic acid is dissolved.in- 100 parts of water and added to a dyebath of 2900 parts of water.The. further addition is made of 2 parts of anhydrous sodium carbonateand 60 parts of a solution consisting of parts of copper tartrate, 100parts of monoethanolamine and 900 parts of water and 100 parts ofwettedout cotton are entered at about C. The bath temperature is raisedwithin hour to boiling and dyeing carried out at. the boil for 4; hour,during which time, after 5 and after 20 minutes, in each case 20 partsof crystalline sodium sulphate are added. After this time the bath iscompletely exhausted and the resulting pure greenish blue exhibits anexcellent fastness to washing and light.

If the parts of ethanolamine in the above process are replaced by 100parts of concentrated ammonia (24 per cent.) or 100 parts ofhydroxyethyl-isopropylamine, similar results are obtained.

.If 1 part is employed of the dyestuff which is obtained from the disazodyestufi of the formula HOJS- ts Ht by reduction with glucose inalkaline solution and otherwise the process is conducted as abovedescribed, a very level bluish grey is obtained of good fastness towashing. Without thereby altering the result, the 50 parts of coppertartrate can be replaced by 50 parts of crystalline copper nos HOOC

plex copper compound of an aliphatic hydroxycarboxylic acid, the mixtureof said complex copper compound and said aliphatic amine being stable inthe dyebath during the dyeing process.

2. A process for dyeing undyed cellulosic textile fibers withdifiicultly water-soluble copper compounds of dyestufis which comprisessubjecting the said fibers to the action of a dyebath preparedessentially from a copper-free dyestuil forming the basis for the coppercompound, a water soluble purely aliphatic amine which cannot besubstantially removed from the dyebath with steam and a complex coppercompound of an. aliphatic hydroxycarboxylic acid, the mixture of saidcomplex copper compound and said aliphatic aminev being stable in thedyebath during the dyeing process.

3., A process for dyeing undyed cellulosic textile fibers withdiflicultly water-soluble copper compounds, of dyestufis. whichcomprises subiecting the, said, fibers to the action of a dyebathprepared essentially from a copper-free dyestufi containing at least twoazov groups and at least once. the atom grouping in which A representsan aromatic radical and B represents a cyclic radical, of which radicalsthe carbon atoms shown dorm part of the ring structure, a water-solublepurely aliphatic amine which cannot be substantially removed from thedyebath with steam and a complex copper compound of an aliphatichydroxycarboxylic acid, the mixture of said complex copper compound andsaid aliphatic amine being stable in the dyebath during the dyeingprocess.

4. A process for dyeing undyed cellulosic textile fibers withdifficultly water-soluble copper compounds of dyestuils which comprisessub-' jecting the said fibers to the action of a dyebath preparedessentially from a copper-free dyestuff containing at least two azogroups and at least once the atom grouping -Z il v jecting the saidfibers to the action of a dyebath prepared essentially from thecopper-free dyestufi of the formula 13 a water soluble purely aliphaticamine which cannot be substantially removed from the dyebath with steamand a complex copper compound of an aliphatic hydroxycarboxylic acid,the mixture of said complex copper compound and said 5 aliphatic aminebeing stable in the dyebath during the dyeing process.

6. A process for dyeing undyed cellulosic textile fibers withdiiiicultly water-soluble copper compounds of dyestuffs which comprisessubjecting the said fibers to the action of a dyebath preparedessentially from the copper-free dye- 20 stuff of the formula S OzNH;

a Water-soluble purely aliphatic amine which cannot be substantiallyremoved from the dyebath with steam and a complex copper compound of analiphatic hydroxycarboxylic acid. the mixture of said complex coppercompound a water-soluble purely aliphatic amine which 35 and saidaliphatic amine being stable in the dyecannot be substantially removedfrom the dyebath with steam and a complex copper compound of analiphatic hydroxycarboxylic acid, the mixture of said complex coppercompound and said aliphatic amine being stable in the dyebath dur- 0 ingthe dyeing process.

bath during the dyeing process.

HENRI RIA'I. WALTER ANDERAU. JACQUES WEGMANN. HANS MAYER. KARL MENZI.

file of this patent:

UNITED STATES PATENTS Number Name 2,148,659 Straub 2,185,905 'StraubDate Feb. 28, 1939 Jan. 2, 1940

1. A PROCESS FOR DYEING UNDYED CELLULOSIC TEXTILE FIBERS WITH DIFFICULTY WATER-SOLUBLE COPPER COMPOUNDS OF DYESTUFFS WHICH COMPRISES SUBJECTING SAID FIBERS TO THE ACTION OF A DYEBATH PREPARED ESSENTIALLY FROM A COPPER-FREE DYESTUFF FORMING THE BASIS FOR THE COPPER COMPOUND, A WATER SOLUBLE PURELY ALIPHATIC AMINE AND A COMPLEX COPPER COMPOUND OF AN ALIPHATIC HYDROXYCARBOXYLIC ACID, THE MIXTURE OF SAID COMPLEX COPPER COMPOUND AND SAID ALIPHATIC AMINE BEING STABLE IN THE DYEBATH DURING THE DYEING PROCESS. 